WO2003091300A1 - Aqueous polymer dispersions, based on copolymers of vinyl aromatics and butadiene, method for their production and their use as sizing agents for paper - Google Patents
Aqueous polymer dispersions, based on copolymers of vinyl aromatics and butadiene, method for their production and their use as sizing agents for paper Download PDFInfo
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- WO2003091300A1 WO2003091300A1 PCT/EP2003/003898 EP0303898W WO03091300A1 WO 2003091300 A1 WO2003091300 A1 WO 2003091300A1 EP 0303898 W EP0303898 W EP 0303898W WO 03091300 A1 WO03091300 A1 WO 03091300A1
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- butadiene
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
Definitions
- the invention relates to aqueous polymer dispersions based on copolymers of vinylaromatics and butadiene, processes for their preparation and their use as mass and surface sizing agents for paper.
- aqueous polymer dispersions as sizing agents and as coating agents for paper is already known.
- starch and / or starch derivatives to stabilize the polymer particles of such sizing agents is also described in the literature.
- JP-A-58/115, 196 describes the preparation of graft copolymers which are obtained by polymerizing 5-85% by weight of styrene and 2-50% by weight of (meth) acrylates in the presence of water-soluble polymers, such as starch, are available.
- the aqueous dispersions which can be prepared in this way are used as sizes for paper.
- EP-A-0 257 412 discloses sizing agents for paper which are obtained by polymerizing a monomer mixture of 20-65% by weight of acrylonitrile, 80-35% by weight of at least one acrylic acid ester and 0-10% by weight of others ethylenically unsaturated monomers are available in the aqueous phase in the presence of a degraded starch with a reduced viscosity of 0.12-0.5 dl / g and redox initiators.
- sizing agents based on copolymers of acrylonitrile and acrylic acid esters are obtained by polymerizing the monomers in an aqueous medium in the presence of a degraded starch with a reduced viscosity of 0.04 to less than 0.12 dl / g and made by redox catalysts.
- EP-A-0 307 816 discloses a process for improving the printability of paper, in which an aqueous coating composition comprising a pigment, a cationic aqueous polymer dispersion of a paper sizing agent and a surface-active substance and / or a polymeric dispersing agent which interfere with the formation of the surface sizing apply to the surface of the paper on one or both sides.
- EP-A-0 735 065 describes the preparation of a photomeric polymer dispersion by means of a two-stage polymerization.
- ethylenically unsaturated monomers and up to 30% by weight of unsaturated carboxylic, sulfonic or phosphonic acids are poly erized in the presence of enzymatically or hydrolytically degraded starch and / or starch derivatives.
- ethylenically unsaturated monomers and up to 35% by weight cationic monomers are polymerized.
- DE-A-198 53 489 relates to the use of aqueous styrene / butadiene dispersions, which are prepared by radical polymerization of styrene and butadiene in the presence of protective colloids such as polyvinyl alcohol or water-soluble polysaccharides, in building adhesive formulations.
- protective colloids such as polyvinyl alcohol or water-soluble polysaccharides
- the object of the invention is to provide new materials which are suitable, for example, for the size and surface sizing of paper.
- the invention also relates to a process for the preparation of aqueous copolymer dispersions based on vinyl aromatics and butadiene by copolymerizing vinyl aromatics and butadiene in an aqueous medium in the presence of starch and water-soluble redox catalysts, which is characterized in that the copolymerization
- a monomer mixture is preferably polymerized
- a redox catalyst made of hydrogen peroxide and heavy metal ions from the group of the cerium, manganese and iron (II) salts.
- the invention also relates to the use of the aqueous polymer dispersions described above as mass and / or surface sizing agents for paper, cardboard and cardboard.
- Examples of monomers of group (a) are styrene and substituted styrenes such as ⁇ -methylstyrene and mixtures of the monomers mentioned.
- the monomer mixture used in the polymerization preferably contains the vinyl aromatics of group (a) in an amount of 50.0 to 99.9% by weight, in particular 75 to 99% by weight.
- Styrene is preferably used as the vinyl aromatic in the copolymerization.
- Suitable monomers of group (b) are 1,3-butadiene and substituted butadienes such as 2-chloro-butadiene or mixtures thereof.
- the monomers of group (b) are preferably present in the monomer mixture in an amount of 0.1 to 50% by weight, particularly preferably 1 to 25% by weight.
- Suitable as monomers of group (c) are anionic, cationic and / or non-ionic hydrophilic ethylenically unsaturated monomers.
- anionic monomers are: acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, vinyl acetic acid,
- the suitable monomers (c) are preferably water-soluble. For example, they have a solubility of at least 50 g / 1 water at a temperature of 20 ° C.
- Suitable monomers (c) are, for example, acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinyloxazolidone, methylpolyglycol acrylates, methylpolyglycol methacrylates.
- Suitable cationic monomers are e.g. Dialkylaminoalkyl acrylates, esters and / or methacrylamides and / or methacrylic esters. Examples of these are esters of ethylenically unsaturated
- Carboxylic acids with amino alcohols such as dimethylaminoethyl acrylate, dimethyla inoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dirnethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate.
- the basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the sulfonic acids or in quaternized form.
- Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
- Suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids with alkyl residues of 1 to 6 carbon atoms, e.g. N-methyl acrylamide, N, N-di-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propyl acrylamide and tert. -Butyl acrylamide and basic (meth) acrylic amides, e.g.
- N-vinylimidazole and substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-Vi nyl-2-ethylimidazole and N-vinylimidazolines such as N-vinyl-imidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethyl-imidazoline.
- N-vinylimidazoles and N-vinylimidazolines are also used in neutralized or in quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.
- the following are also suitable as comonomers:
- N-Trimethylammoniumethylacrylamidchlorid N-Trimethylammoniume- thylmethacrylamidchlorid, N-Trimethylammoniumethylmethacryle- sterChlorid, N-Trimethylammoniumethylacrylesterchlorid, trimethylol lammoniumethylacrylamidmethosulfat, crylamidmethosulfat Trimethylammoniumethylmetha-, N-Ethyldimethylamoniummethylacrylamidetho- sulfate, N-ethyl-dimethylammoniumethylmethacrylamidethosulfat, trimethylammonium propylacrylamidchlorid, Trimethylaamoniumpro- pylmethotfura pylmethotfura pylmethotfuramidmethosulfat, Trimethylammoniumpropylacrylamidmethosulfat , Trimethylammoniumpropylmethacrylamidmethosulfat and N-Ethyldimethylam
- Monomers of group (c) used with preference are acrylic acid, methacrylic acid, maleic acid, N-vinylformamide, acrylic acid and methacrylic acid esters and vinyl acetate.
- native starches such as potato, wheat, corn, rice or tapioca starch can be considered as starch, with potato starch being preferred.
- Starches with an amylopectin content of at least 80% are preferred.
- chemically modified starches such as hydroxyethyl or hydroxypropyl starches or starches which contain anionic groups, e.g. Phosphate starch, or also cationic starches, which have quaternary ammonium groups.
- the starch to be used according to the invention is obtained by subjecting the starch types mentioned to an oxidative, thermal, acidic or enzymatic degradation.
- the starch can also be subjected to a combined breakdown, e.g. hydrolytic and oxidative degradation.
- a combined breakdown e.g. hydrolytic and oxidative degradation.
- hydrolytic and oxidative degradation In order to set the desired molecular weight of the starch, it is preferably degraded enzymatically.
- a starch breakdown with Termamyl as is usually carried out to improve the dissolving properties of the starch, and a further breakdown e.g. B. with hydrogen peroxide, the z. B. can be carried out shortly before the subsequent graft copolymerization.
- hydrogen peroxide (calculated as 100%) is used in concentrations of, for example, 0.3 to 5.0% by weight, based on the starch used.
- the amount of hydrogen peroxide depends on the molecular weight up to which the starch should be broken down.
- the starches degraded in this way have an average molecular weight Mn of 500 to 40,000, preferably 500 to 10,000, which on the one hand ensures good dispersion of the emulsion polymers and on the other hand prevents the polymerization batch from precipitating. is avoided.
- the average molecular weight of the degraded starch can easily be determined using known methods using gel chromatography analysis methods after calibration, e.g. B. with dextran standards. Suitable for characterization are also viscometric methods, such as those used for. B. are described in "Methods in Carbohydrate Chemistry"; Volume IV, Academic Press New York and Frankfurt, 1964, p. 127.
- the intrinsic viscosity of the degraded starches thus determined is preferably 0.05 to 0.12 dl / g.
- the polymerization of the monomers (a), (b) and optionally (c) is generally carried out in such a way that both the monomers, either individually or as a mixture, are added to the aqueous solution of the degraded starch, and also that used to initiate the polymerization eligible redox initiator.
- anionic or nonionic low molecular weight emulsifiers such as sodium alkyl sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sulfosuccinate, fatty alcohol polyglycol ether, alkylaryl polyglycol ether etc. can be added to the polymerization batch.
- emulsifiers generally impair the sizing effect of the polymer dispersions and usually lead to undesirable foaming when handling the dispersions.
- the polymerization is therefore preferably carried out without an emulsifier.
- polymeric anionic emulsifiers which contain sulfonic acid groups, for. B. based on maleic anhydride copolymers.
- the polymerization is usually carried out in the absence of oxygen, preferably in an inert gas atmosphere, for. B. under nitrogen. Ensure thorough mixing with a suitable stirrer during the polymerization.
- the polymerization can be carried out either in the feed process or in a batch process, e.g. at temperatures between 30 and 100 ° C, preferably between 70 and 95 ° C.
- the monomers and the radical initiator are evenly metered into the starch solution in a stirred tank.
- the Reak tion times are, for example, between 0.5 and 10 hours, preferably between 0.75 and 4 hours.
- Graft-active waterless redox systems are suitable for initiating the polymerization.
- conventional water-soluble starters such as potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide etc.
- at least one conventional reducing agent such as sodium sulfite, sodium disulfite, sodium bisulfite, sodium dithionite, ascorbic acid and the sodium salt of the hydroxoxymethanesulfonic system as redox methanesulfonic acid system.
- sodium sulfite sodium disulfite
- sodium bisulfite sodium bisulfite
- sodium dithionite sodium salt of the hydroxoxymethanesulfonic system
- ascorbic acid sodium salt of the hydroxoxymethanesulfonic system
- sodium salt of the hydroxoxymethanesulfonic system as redox methanesulfonic acid system.
- such redox systems lead to coarser dispersions.
- redox catalysts with high grafting activity are water-soluble starter systems such as redox systems made of hydrogen peroxide and heavy metal ions such as cerium, manganese or iron (II) salts, such as those e.g. in Houben-Weyl "Methods of Organic Chemistry 4th Edition, Volume E20, p. 2168" are described.
- the redox system consisting of hydrogen peroxide and an iron (II) salt such as iron (II) sulfate, which provides finely divided dispersions with a high graft yield, is particularly suitable.
- the graft yield is understood to mean the proportion of the polymer which is chemically coupled to the starch after the end of the polymerization.
- the grafting yield should be as high as possible to achieve finely divided and effective dispersions.
- the polymerization is usually carried out so that the heavy metal salt of the redox system such.
- the iron (II) salt is added to the batch before the polymerization, while hydrogen peroxide is metered in simultaneously with the monomers, but separately therefrom.
- Iron (II) salt is usually used in concentrations of 10 to 200 mg / 1 Fe ++ ion, based on the total dispersion, although higher and lower concentrations are also possible.
- Hydrogen peroxide (calculated as 100%) is added in amounts of, for example, 0.2 to 6.0% by weight, based on the monomer. This amount is in addition to the amount of hydrogen peroxide used to break down starch.
- redox initiators In addition to the redox initiators, conventional starters such as oil-soluble or only slightly water-soluble organic peroxides or azo initiators can also be used.
- further reducing agents which are preferably introduced with the iron salt before the polymerization, is particularly advantageous.
- a reducing agent such as B. sodium sulfite, sodium disulfite, sodium Hydrogen sulfite, sodium dithionite, ascorbic acid and the sodium salt of hydroxymethanesulfonic acid in question.
- the molecular weight of the grafted-on polymer can also be adjusted by using chain transfer agents or regulators such as. B. n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan or t-butyl mercaptan. Odor-free regulators such as terpinolene are particularly suitable, cf. EP-A-1,191,044th
- the polymerization is usually carried out at pH values from 2.5 to 9, preferably in the weakly acidic range at pH values from 3 to 5.5.
- the pH can be adjusted to the desired value before or during the polymerization with customary acids such as hydrochloric acid, sulfuric acid or acetic acid or with bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia, ammonium carbonate etc. It is preferred to adjust the pH of the aqueous polymer dispersions to 5 to 7 after the polymerization by adding sodium hydroxide solution, potassium hydroxide solution or ammonia.
- concentration of the dispersions according to the invention is, for example, 10 to 40% by weight, preferably 18 to 40% by weight.
- a 25% aqueous polymer dispersion for example, has a viscosity of 3 and 300 mPa • s.
- the dispersions of the invention have a very low
- Particle size e.g. it is below 120 nm.
- the average particle size of the dispersed polymer particles is preferably 50 to 100 nm.
- B. can be determined by laser correlation spectroscopy or by turbidity measurement.
- complexing agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, polyaspartic acid, iminodisuccinic acid, citric acid or their alkali metal or ammonium salts are, for example, suitable for this.
- the amount of complexing agent used depends on the amount of heavy metal salt to be complexed.
- the complexing agents are usually used in an amount of 1 to 10 mol, preferably 1.1 to 5 mol, per mol of heavy metal ion.
- the polymer dispersions according to the invention are preferably used as surface sizing agents, but can also be used as mass sizing agents. They usually assign one weakly anionic charge character and have only a slight tendency to foam. They are suitable for surface sizing of all paper grades manufactured in practice, e.g. B. of alum-containing, alum-free, filled with kaolin or chalk papers as well as ground paper containing wood pulp or waste paper, which can be both acidic and neutral or alkaline and which are unsized or in the pulp z. B. can be pre-glued with alkyl ketene dimer or alkenyl succinic anhydride.
- the dispersions according to the invention can be processed using all the process methods customary for surface sizing and can be applied to the surface of paper in the size press liquor. It is customary to use it in aqueous solution together with 5 to 20% by weight of starch and, if appropriate, pigments and optical brighteners in the size press or in modern application units such as film press, speedsizer or gate roll.
- the amount of sizing agent in the fleet depends on the desired degree of sizing of the papers to be finished.
- the concentration of the dispersions according to the invention in the liquor is usually between 0.1 and 2.0% by weight of solid substance, preferably between 0.2 and 1.0% by weight.
- the amount applied to the paper is determined by the wet absorption of the optionally pre-sized papers. As a wet pickup is to be understood the amount of size press liquor that can be absorbed by the dry pulp and that u. a. can be influenced by the pre-sizing in the paper pulp. Depending on the wet absorption, the amount of sizing agent absorbed by the paper is in most cases 0.03 to 1.2
- % By weight of solid substance, based on dry fibrous material, preferably between 0.1 and 0.8% by weight.
- the size press liquors can also contain finely divided pigments to improve printability, such as. B. chalk, precipitated calcium carbonate, kaolin, titanium dioxide, barium sulfate or gypsum.
- finely divided pigments such as. B. chalk, precipitated calcium carbonate, kaolin, titanium dioxide, barium sulfate or gypsum.
- optical brighteners to increase the degree of whiteness is also customary, if appropriate with the addition of carriers such as. B. polyethylene glycol, polyvinyl alcohol or polyvinyl pyrrolidone.
- the good compatibility of the dispersions according to the invention with optical brighteners is particularly advantageous, so that papers with a high degree of whiteness can be obtained.
- the insensitivity of the dispersions according to the invention to the addition of electrolytes such as Na, Ca or Al ions, which in many cases, for. B. by Migra tion from the raw paper to be processed can be contained in the size press fleet or can be added specifically to increase the conductivity.
- the sizing agent dispersions according to the invention are particularly suitable for the production of graphic papers which are used for all customary modern printing processes.
- inkjet printing z. B. a high ink adsorption capacity and fast drying without strikethrough with a good ink hold-out, maintaining high color density and high resolution as well as good smudge and water resistance.
- a high degree of edge sharpness is required in color printing, whereby the individual color inks must not run into one another and should have a high color strength, brilliance and light fastness.
- toner adhesion is required for the use of the papers equipped with the dispersions according to the invention in electrophotographic printing processes, such as in laser printers and copiers.
- H. the toner must adhere to the paper with high smudge resistance.
- This requirement can also be met by using the dispersions according to the invention, in particular on z.
- B. pre-glued papers with alkyl diketene can be met in an excellent manner.
- a 10% strength aqueous tert-butyl hydroperoxide solution was metered in at 60 ° C. in the course of 60 minutes. Then the dispersion was mixed with 0.225 kg of a 40% Trilon B solution and 1.2 kg of a 25% aqueous sodium hydroxide solution and then physically deodorized for 4 hours at 10 kg steam per hour. An aqueous dispersion with a solids content of 40%, an LD value of 80 and a particle diameter of 114 nm was obtained.
- reaction mixture 20 of the monomer and the hydrogen peroxide addition, the reaction mixture was polymerized for a further hour at 85.degree. A cationic dispersion with a solids content of 34% and an LD value of 86 was obtained.
- aqueous polymer dispersions prepared according to Examples 1 and 2 and Comparative Examples 1 to 5 were tested for their effectiveness as surface sizing agents for paper.
- the Cobb value was determined in accordance with DIN 53132 and the ink floating time in accordance with DIN 53126.
- a non-pre-sized paper filled with PCC (precipitated calcium carbonate) made of 70% birch and 30% pine sulfate was used as the test paper.
- PCC precipitated calcium carbonate
- aqueous polymer dispersions were each diluted to a polymer content of 2 g / 1 and applied to the test paper described above using a size press. The test papers were then dried, air-conditioned and tested using the methods mentioned above. The determined
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/510,279 US7662871B2 (en) | 2002-04-24 | 2003-04-15 | Aqueous polymer dispersions, based on copolymers of vinyl aromatics and butadiene, method for their production and their use as sizing agents for paper |
AU2003226809A AU2003226809A1 (en) | 2002-04-24 | 2003-04-15 | Aqueous polymer dispersions, based on copolymers of vinyl aromatics and butadiene, method for their production and their use as sizing agents for paper |
EP03747101A EP1501880B1 (en) | 2002-04-24 | 2003-04-15 | Aqueous polymer dispersions, based on copolymers of vinyl aromatics and butadiene, method for their production and their use as sizing agents for paper |
CA002481797A CA2481797A1 (en) | 2002-04-24 | 2003-04-15 | Aqueous polymer dispersions, based on copolymers of vinyl aromatics and butadiene, method for their production and their use as sizing agents for paper |
JP2003587856A JP2005528478A (en) | 2002-04-24 | 2003-04-15 | Aqueous polymer dispersions based on copolymers of vinyl aromatic compounds and butadiene, processes for their preparation and their use as sizing agents for paper |
DE50302436T DE50302436D1 (en) | 2002-04-24 | 2003-04-15 | Aqueous polymer dispersions based on vinylaromatics and butadiene copolymer, process for their preparation and their use as saponification agent for paper |
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DE10218418.6 | 2002-04-24 | ||
DE10218418A DE10218418A1 (en) | 2002-04-24 | 2002-04-24 | Aqueous polymer dispersions based on copolymers of vinyl aromatics and butadiene, processes for their preparation and their use as sizes for paper |
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WO2003091300A1 true WO2003091300A1 (en) | 2003-11-06 |
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US (1) | US7662871B2 (en) |
EP (1) | EP1501880B1 (en) |
JP (1) | JP2005528478A (en) |
AT (1) | ATE317863T1 (en) |
AU (1) | AU2003226809A1 (en) |
CA (1) | CA2481797A1 (en) |
DE (2) | DE10218418A1 (en) |
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- 2003-04-15 WO PCT/EP2003/003898 patent/WO2003091300A1/en active IP Right Grant
- 2003-04-15 DE DE50302436T patent/DE50302436D1/en not_active Expired - Lifetime
- 2003-04-15 AU AU2003226809A patent/AU2003226809A1/en not_active Abandoned
- 2003-04-15 AT AT03747101T patent/ATE317863T1/en not_active IP Right Cessation
- 2003-04-15 CA CA002481797A patent/CA2481797A1/en not_active Abandoned
- 2003-04-15 JP JP2003587856A patent/JP2005528478A/en not_active Withdrawn
- 2003-04-15 US US10/510,279 patent/US7662871B2/en not_active Expired - Fee Related
- 2003-04-15 EP EP03747101A patent/EP1501880B1/en not_active Expired - Lifetime
- 2003-04-15 ES ES03747101T patent/ES2257686T3/en not_active Expired - Lifetime
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EP0408099A1 (en) * | 1989-07-11 | 1991-01-16 | Synthomer Chemie Gmbh | Process for producing aqueous polymer dispersions |
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WO2006008056A1 (en) * | 2004-07-20 | 2006-01-26 | Basf Aktiengesellschaft | Method for the production of aqueous styrol-butadiene polymer dispersions |
EP2949699A1 (en) | 2006-08-18 | 2015-12-02 | Styrolution Europe GmbH | Process to prepare thermoplastic molding compositions based on acrylonitrile, styrene, and butadiene, comprising a thermoplastic copolymer and a grafted copolymer |
WO2009047233A1 (en) * | 2007-10-08 | 2009-04-16 | Basf Se | Aqueous polymer dispersions based on copolymers formed from vinylaromatics and conjugated aliphatic dienes, processes for preparation thereof and use thereof |
US8003716B2 (en) | 2007-10-08 | 2011-08-23 | Basf Se | Aqueous polymer dispersions based on copolymers formed from vinylaromatics and conjugated aliphatic dienes, processes for preparation thereof and use thereof |
US9074322B2 (en) | 2008-04-03 | 2015-07-07 | Basf Se | Paper coating or binding formulations and methods of making and using same |
US8329803B2 (en) | 2008-11-25 | 2012-12-11 | Basf Se | Process for the preparation of aqueous polymer dispersions from a aromatic compound, a conjugated aliphatic diene and an ethylenically unsaturated carbonitrile |
US8530563B2 (en) | 2008-11-25 | 2013-09-10 | Basf Se | Process for the preparation of aqueous polymer dispersions from a aromatic compound, a conjugated aliphatic diene and an ethylenically unsaturated carbonitrile |
WO2017032720A1 (en) | 2015-08-25 | 2017-03-02 | Basf Se | White polymer dispersion |
Also Published As
Publication number | Publication date |
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AU2003226809A1 (en) | 2003-11-10 |
DE10218418A1 (en) | 2003-11-06 |
EP1501880A1 (en) | 2005-02-02 |
ATE317863T1 (en) | 2006-03-15 |
EP1501880B1 (en) | 2006-02-15 |
CA2481797A1 (en) | 2003-11-06 |
US20050176878A1 (en) | 2005-08-11 |
DE50302436D1 (en) | 2006-04-20 |
US7662871B2 (en) | 2010-02-16 |
ES2257686T3 (en) | 2006-08-01 |
JP2005528478A (en) | 2005-09-22 |
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